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Publication numberUS7767853 B2
Publication typeGrant
Application numberUS 11/975,141
Publication dateAug 3, 2010
Filing dateOct 17, 2007
Priority dateOct 20, 2006
Fee statusPaid
Also published asUS20080249335
Publication number11975141, 975141, US 7767853 B2, US 7767853B2, US-B2-7767853, US7767853 B2, US7767853B2
InventorsAshok L. Cholli, Rajesh Kumar, Taizoon Canteenwala, Vijayendra Kumar
Original AssigneePolnox Corporation
Export CitationBiBTeX, EndNote, RefMan
External Links: USPTO, USPTO Assignment, Espacenet
Antioxidants and methods of making and using the same
US 7767853 B2
Abstract
The present invention is directed to a compound represented by Structural Formula I:

wherein the variables are described herein. Also included are methods of making the compounds of Structural Formula (I) and methods of using the compounds as antioxidants.
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Claims(33)
1. A compound represented by Structural Formula I:
wherein:
R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;
Z is —C(O)NRc—, —NRcC(O)—, —NRc—, —CRc═N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC(O)— or a bond;
Rc is independently H or optionally substituted alkyl;
Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, —SH;
Rb, for each occurrence, is independently H or optionally substituted alkyl;
s, for each occurrence, is independently integers from 0 to 4; and
m and n, for each occurrence, are independently integers from 0 to 6.
2. The compound of claim 1, wherein:
Z is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —O— or —C(O)—;
Rb is H;
Ra, for each occurrence is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl;
n and m, for each occurrence, are independently integers from 0 to 2; and
s, for each occurrence, is independently an integer from 0 to 2.
3. The compound of claim 2, wherein:
Z is —C(O)NH— or —NHC(O)—;
Ra, for each occurrence is independently an alkyl or an alkoxycarbonyl;
and s is 2.
4. The compound of claim 3, wherein each Ra is independently an alkyl group.
5. The compound of claim 1, wherein the compound is represented by Structural Formula II:
wherein:
R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;
Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, or —SH;
Rb, for each occurrence, is independently H or optionally substituted alkyl.
s, for each occurrence, is independently an integer from 0 to 4; and
m, for each occurrence, is independently an integer from 0 to 6.
6. The compound of claim 5, wherein:
Ra, for each occurrence, is independently an optionally substituted alkyl;
Rb is H;
s, for each occurrence, is independently an integer from 0 to 2; and
m, for each occurrence, is independently an integer from 0 to 2.
7. The compound of claim 6, wherein Ra is independently an alkyl and s is 2.
8. The compound of claim 1, wherein the compound is represented by Structural Formula III:
wherein:
R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H.
9. The compound of claim 8, wherein R and R′ are H.
10. The compound of claim 8, wherein R is H and R′ is an alkyl.
11. The compound of claim 10, wherein R′ is a C1-C15 alkyl.
12. The compound of claim 11, wherein R′ is a C10 alkyl.
13. The compound of claim 12, wherein R′═—(CH2)9CH3.
14. A method of inhibiting oxidation in an oxidizable material comprising combining the oxidizable material with a compound represented by Structural Formula I
wherein:
R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;
Z is —C(O)NRc—, —NRcC(O)—, —NRc—, —CRc═N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC(O)— or a bond;
Rc is independently H or optionally substituted alkyl;
Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, —SH;
Rb, for each occurrence, is independently H or optionally substituted alkyl;
s, for each occurrence, is independently an integer from 0 to 4; and
m and n, for each occurrence, are independently integers from 0 to 6.
15. The method of claim 14, wherein
Z is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —O— or —C(O)—;
Rb is H;
Ra, for each occurrence is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl;
n and m, for each occurrence, are independently integers from 0 to 2; and
s, for each occurrence, is independently an integer from 0 to 2.
16. The method of claim 15, wherein:
Z is —C(O)NH— or —NHC(O)—;
Ra, for each occurrence is independently an alkyl or an alkoxycarbonyl;
and s is 2.
17. The method of claim 16, wherein each Ra is independently an alkyl group.
18. The method of claim 14, wherein the compound is represented by Structural Formula II:
wherein:
R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;
Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, or —SH;
Rb, for each occurrence, is independently H or optionally substituted alkyl.
s, for each occurrence, is independently an integer from 0 to 4; and
m, for each occurrence, is independently an integer from 0 to 6.
19. The method of claim 18, wherein:
Ra, for each occurrence, is independently an optionally substituted alkyl;
Rb is H;
s, for each occurrence, is independently an integer from 0 to 2; and
m, for each occurrence, is independently an integer from 0 to 2.
20. The method of claim 19, wherein Ra is independently an alkyl and s is 2.
21. The method of claim 14, wherein the compound is represented by Structural Formula III:
wherein:
R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H.
22. The method of claim 21, wherein R and R′ are H.
23. The method of claim 21, wherein R is H and R′ is an alkyl.
24. The method of claim 23, wherein R′ is a C1-C15 alkyl.
25. The method of claim 24, wherein R′ is a C10 alkyl.
26. The method of claim 25, wherein R′═—(CH2)9CH3.
27. The method of claim 14, wherein the oxidizable material is an organic polymer or plastic.
28. The method of claim 14, wherein the oxidizable material is an elastomer.
29. The method of claim 14, wherein the oxidizable material is a lubricant.
30. The method of claim 14, wherein the oxidizable material is a petroleum based product.
31. The method of claim 14, wherein the oxidizable material is an edible oil or cooking oil.
32. The method of claim 14, wherein the oxidizable material is a cosmetic.
33. The method of claim 14, wherein the oxidizable material is a processed food product.
Description
RELATED APPLICATION(S)

This application claims the benefit of U.S. Provisional Application No. 60/853,275, filed on Oct. 20, 2006. The entire teachings of the above application are incorporated herein by reference.

BACKGROUND OF THE INVENTION

Antioxidants are employed to prevent oxidation in a wide range of materials, for example, plastics, elastomers, lubricants, petroleum based products (lubricants, gasoline, aviation fuels, and engine oils), cooking oil, cosmetics, processed food products, and the like. While many antioxidants exist, there is a continuing need for new antioxidants that have improved properties.

SUMMARY OF THE INVENTION

The present invention relates to antioxidant that in general have improved antioxidant properties.

In one embodiment the present invention is directed to compounds represented by Structural Formula I:


wherein:

R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;

Z is —C(O)NRc—, —NRcC(O)—, —NRc—, —CRc═N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC(O)— or a bond;

Rc is independently H or optionally substituted alkyl;

Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, —SH;

Rb, for each occurrence, is independently H or optionally substituted alkyl;

s, for each occurrence, is independently an integer from 0 to 4; and

m and n, for each occurrence, are independently integers from 0 to 6.

In another embodiment, the present invention is directed to a compound represented by Structural Formula II:


wherein:

R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;

Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, or —SH;

Rb, for each occurrence, is independently H or optionally substituted alkyl.

s, for each occurrence, is independently an integer from 0 to 4; and

m, for each occurrence, is independently an integer from 0 to 6.

In another embodiment, the present invention is directed a compound represented by Structural Formula III:


wherein R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H.

In another embodiment the present invention is directed to methods of inhibiting oxidation in an oxidizable material comprising combining the oxidizable material with a compound represented Structural Formula I, II or III.

In certain embodiments, the compounds of the present invention can have enhanced antioxidant activity and better thermal stability compared to commercially available antioxidants.

BRIEF DESCRIPTION OF THE DRAWINGS

The foregoing and other objects, features and advantages of the invention will be apparent from the following more particular description of preferred embodiments of the invention, as illustrated in the accompanying drawings in which like reference characters refer to the same parts throughout the different views. The drawings are not necessarily to scale, emphasis instead being placed upon illustrating the principles of the invention.

FIG. 1 is a graph showing oxidation induction time of compound A measured according to ASTM procedure.

DETAILED DESCRIPTION OF THE INVENTION

In certain embodiments the compounds of the present invention comprise sterically hindered groups such as phenol groups. Sterically hindered, as used herein means that the substituent group (e.g., bulky alkyl group) on a ring carbon atom adjacent (or alternatively para) to a ring carbon atom substituted with a phenolic hydroxy group (or thiol or amine group), is large enough to sterically hinder the phenolic hydroxy group (or thiol or amine groups). This steric hindrance, in certain embodiments results in more labile or weak bonding between the oxygen and the hydrogen (or sulfur or nitrogen and hydrogen) and in turn enhances the stability and antioxidant activity (proton donating activity) of the sterically hindered antioxidant.

The antioxidants of the invention include substituted benzene molecules. Some of these benzene molecules are typically based on phenol or a phenol derivative, such that they have at least one hydroxyl or ether functional group. In certain embodiments, the benzene molecules have a hydroxyl group. The hydroxyl group can be a free hydroxyl group and can be protected or have a cleavable group attached to it (e.g., an ester group). Such cleavable groups can be released under certain conditions (e.g., changes in pH), with a desired shelf life or with a time-controlled release (e.g., measured by the half-life), which allows one to control where and/or when an antioxidant can exert its antioxidant effect. The antioxidants can also include analogous thiophenol and aniline derivatives, e.g., where the phenol —OH can be replaced by —SH, —NH—, and the like.

Substituted benzene in an antioxidant of the present invention are also typically substituted with a bulky alkyl group or an n-alkoxycarbonyl group. In certain embodiments, the benzene group is substituted with a bulky alkyl group. In certain other embodiments, the bulky alkyl group is located ortho or meta to a hydroxyl group on the benzene ring, typically ortho. A “bulky alkyl group” is defined herein as an alkyl group that is branched alpha- or beta- to the benzene ring. In certain other embodiments, the alkyl group is branched alpha to the benzene ring. In certain other embodiments, the alkyl group is branched twice alpha to the benzene ring, such as in a tert-butyl group. Other examples of bulky alkyl groups include isopropyl, 2-butyl, 3-pentyl, 1,1-dimethylpropyl, 1-ethyl-1-methylpropyl and 1,1-diethylpropyl. In certain other embodiments, the bulky alkyl groups are unsubstituted, but they can be substituted with a functional group that does not interfere with the antioxidant activity of the molecule. Straight chained alkoxylcarbonyl groups include methoxycarbonyl, ethoxycarbonyl, n-propoxycarbonyl, n-butoxycarbonyl and n-pentoxycarbonyl. N-propoxycarbonyl is a preferred group. Similar to the bulky alkyl groups, n-alkoxycarbonyl groups are optionally substituted with a functional group that does not interfere with the antioxidant activity of the molecule.

In certain embodiment, the compounds of the present invention are represented by Structural Formula I:

R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H. In certain other embodiment, R and R′ are independently H or alkyl and at least one of R and R′ is H. In certain other embodiment, R and R′ are H. In certain other embodiment, R is H and R′ is optionally substituted alkyl. In certain other embodiment, R is H and R′ is alkyl. In certain other embodiment, R is H and R′ is C1-C10 alkyl. More specifically, R′ is C10 alkyl. Even more specifically, R′ is —(CH2)9CH3.

Z is —C(O)NRc—, —NRcC(O)—, —NRc—, —CRc═N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC(O)— or a bond. In certain other embodiments Z is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —O— or —C(O)—. In certain other embodiments, Z is —C(O)NH— or —NHC(O)—. Optionally, Z is not —C(O)O—, —OC(O)—, —O— or —NH—. In various embodiments, the present invention relates to a compound of Structural Formula I and the attendant definitions, wherein Z is —OC(O)—. In another embodiment, Z is —C(O)O—. In another embodiment, Z is —C(O)NH—. In another embodiment, Z is —NHC(O)—. In another embodiment, Z is —NH—. In another embodiment, Z is —CH═N—. In another embodiment, Z is —C(O)—. In another embodiment, Z is —O—. In another embodiment, Z is —C(O)OC(O)—. In another embodiment, Z is a bond.

Each Rc is independently —H or optionally substituted alkyl. In certain other embodiments Rc is —H or an alkyl group. In certain other embodiments Rc is —H or a C1-C10 alkyl group. In certain other embodiments R′ is —H.

Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, or —SH. In certain other embodiments, each Ra is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl. In certain other embodiment each Ra is independently an alkyl or alkoxycarbonyl. In certain other embodiments each Ra is independently a C1-C6 alkyl or a C1-C6 alkoxycarbonyl. In certain other embodiments each Ra is independently tert-butyl or propoxycarbonyl. In certain other embodiments each Ra is independently an alkyl group. In certain embodiments each Ra is independently a bulky alkyl group. Suitable examples of bulky alkyl groups include butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like. In certain embodiments each Ra is tert-butyl. In certain embodiments at least one Ra adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). In certain other embodiments both Ra groups adjacent to —OH are bulky alkyl groups (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). In another embodiment, both Ra groups are tert-butyl. In another embodiment, both Ra groups are tert-butyl adjacent to the OH group.

Each n and m are independently integers from 0 to 6. In certain embodiments each n and m are independently integers from 0 to 2.

In another embodiment, the present invention relates to a compound of Structural Formula I wherein n is 0.

In another embodiment, the present invention relates to a compound of Structural Formula I wherein m is 0-2.

In another embodiment, the present invention relates to a compound of Structural Formula I and the attendant definitions, wherein n is 0 and m is 2.

In another embodiment, the present invention relates to a compound of Structural Formula I wherein n is 0, m is 2, and Z is —NHC(O)— or —C(O)NH—.

In another embodiment, the present invention relates to a compound of Structural Formula I wherein n is 0, m is 2, Z is —NHC(O)—, and the two R groups adjacent to the OH are tert-butyl.

Each s is independently an integer from 0 to 4. In certain embodiments, each s is independently an integer from 0 to 2. In certain embodiments, s is 2.

In certain embodiment, the compounds of the present invention are represented by Structural Formula II:

R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H. In certain other embodiment, R and R′ are independently H or alkyl and at least one of R and R′ is H. In certain other embodiment, R and R′ are H. In certain other embodiment, R is H and R′ is optionally substituted alkyl. In certain other embodiment, R is H and R′ is alkyl. In certain other embodiment, R is H and R′ is C1-C10 alkyl. More specifically, R′ is C10 alkyl. Even more specifically, R′ is —(CH2)9CH3.

Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, or —SH. In certain other embodiments, each Ra is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl. In certain other embodiment each Ra is independently an alkyl or alkoxycarbonyl. In certain other embodiments each Ra is independently a C1-C6 alkyl or a C1-C6 alkoxycarbonyl. In certain other embodiments each Ra is independently tert-butyl or propoxycarbonyl. In certain other embodiments each Ra is independently an alkyl group. In certain embodiments each Ra is independently a bulky alkyl group. Suitable examples of bulky alkyl groups include butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like. In certain embodiments each Ra is tert-butyl. In certain embodiments at least one Ra adjacent to the —OH group is a bulky alkyl group (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). In certain other embodiments both Ra groups adjacent to —OH are bulky alkyl groups (e.g., butyl, sec-butyl, tert-butyl, 2-propyl, 1,1-dimethylhexyl, and the like). In another embodiment, both Ra groups are tert-butyl. In another embodiment, both Ra groups are tert-butyl adjacent to the OH group.

Each m is independently an integer from 0 to 6. In certain embodiments each m is independently an integer from 0 to 2. In certain embodiment m is 2.

In another embodiment, the present invention relates to a compound of Structural Formula II wherein m is 2 and the two Ra groups adjacent to the OH are tert-butyl.

Each s is independently an integer from 0 to 4. In certain embodiments, each s is independently an integer from 0 to 2. In certain embodiments, s is 2.

In a first embodiment the present invention is directed to a compound represented by Structural Formula I:


wherein:

R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;

Z is —C(O)NRc—, —NRcC(O)—, —NRc—, —CRc═N—, —C(O)—, —C(O)O—, —OC(O)—, —O—, —S—, —C(O)OC(O)— or a bond;

Rc is independently H or optionally substituted alkyl;

Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, —SH;

Rb, for each occurrence, is independently H or optionally substituted alkyl;

s, for each occurrence, is independently an integer from 0 to 4; and

m and n, for each occurrence, are independently integers from 0 to 6.

A second embodiment of the present invention is directed to a compound represented by Structural Formula I, wherein:

Z is —C(O)O—, —OC(O)—, —C(O)NH—, —NHC(O)—, —NH—, —O— or —C(O)—;

Rb is H;

Ra, for each occurrence is independently an optionally substituted alkyl or optionally substituted alkoxycarbonyl;

n and m, for each occurrence, are independently integers from 0 to 2;

s, for each occurrence, is independently an integer from 0 to 2; and the remainder variables are as described above in the first embodiment.

A third embodiment of the present invention is directed to a compound represented by Structural Formula I, wherein:

Z is —C(O)NH— or —NHC(O)—;

Ra, for each occurrence is independently an alkyl or an alkoxycarbonyl;

s is 2; and the remainder of the variables are as described in the second embodiment.

A fourth embodiment of the present invention is directed to a compound represented by Structural Formula I, wherein:

Each Ra is independently an alkyl group, and the remainder of the variables are as described above in the third embodiment. In certain embodiments each Ra is a bulky alkyl group. In certain embodiments two Ra groups are bulky alkyl groups adjacent to the —OH group. In certain embodiments the two R groups are tert-butyl groups adjacent to the —OH group.

A fifth embodiment of the present invention is directed to a compound represented by Structural Formula II, wherein

    • R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H;

Ra, for each occurrence, is independently an optionally substituted alkyl, optionally substituted aryl, optionally substituted alkoxycarbonyl, optionally substituted ester, —OH, —NH2, or —SH;

Rb, for each occurrence, is independently H or optionally substituted alkyl.

s, for each occurrence, is independently an integer from 0 to 4; and

m, for each occurrence, is independently an integer from 0 to 6.

A sixth embodiment of the present invention is directed to a compound Structural Formula II, wherein:

Ra, for each occurrence, is independently an optionally substituted alkyl;

Rb is H;

s, for each occurrence, is independently an integer from 0 to 2;

m, for each occurrence, is independently an integer from 0 to 2; and the remainder of the variables are as described above in the fifth embodiment.

A seventh embodiment of the present invention is directed to a compound represented by Structural Formula II, wherein each Ra is independently an alkyl group, and the remainder of the variables are as described above in the sixth embodiment. In certain embodiments each Ra is a bulky alkyl group. In certain embodiments two Ra groups are bulky alkyl groups adjacent to the —OH group. In certain embodiments the two R groups are tert-butyl groups adjacent to the —OH group.

A eighth embodiment of the present invention is directed to a compound represented by Structural Formula III, wherein R and R′ are independently H or optionally substituted alkyl and at least one of R and R′ is H.

A ninth embodiment of the present invention is directed to a compound represented by Structural Formula III, wherein R is H and R′ is an alkyl. More specifically, R′ is a C1-C10 alkyl. Even more specifically, R′ is a C10 alkyl.

A tenth embodiment of the present invention is directed to a compound A represented by the following structural formula:

A eleventh embodiment of the present invention is directed to compound B represented by the following structural formula:

The term “alkyl” as used herein means a saturated straight-chain, branched or cyclic hydrocarbon. When straight-chained or branched, an alkyl group is typically C1-C20, more typically C1-C10; when cyclic, an alkyl group is typically C3-C12, more typically C3-C7. Examples of alkyl groups include methyl, ethyl, n-propyl, iso-propyl, n-butyl, sec-butyl and tert-butyl and 1,1-dimethylhexyl.

The term “alkoxy” as used herein is represented by —OR**, wherein R** is an alkyl group as defined above.

The term “carbonyl” as used herein is represented by —C(═O)R**, wherein R** is an alkyl group as defined above.

The term “alkoxycarbonyl” as used herein is represented by —C(═O)OR**, wherein R** is an alkyl group as defined above.

The term “aromatic group” includes carbocyclic aromatic rings and heteroaryl rings. The term “aromatic group” may be used interchangeably with the terms “aryl”, “aryl ring” “aromatic ring”, “aryl group” and “aromatic group”.

Carbocyclic aromatic ring groups have only carbon ring atoms (typically six to fourteen) and include monocyclic aromatic rings such as phenyl and fused polycyclic aromatic ring systems in which a carbocyclic aromatic ring is fused to one or more aromatic rings (carbocyclic aromatic or heteroaromatic). Examples include 1-naphthyl, 2-naphthyl, 1-anthracyl and 2-anthracyl. Also included within the scope of the term “carbocyclic aromatic ring”, as it is used herein, is a group in which an aromatic ring is fused to one or more non-aromatic rings (carbocyclic or heterocyclic), such as in an indanyl, phthalimidyl, naphthimidyl, phenanthridinyl, or tetrahydronaphthyl.

The term “heteroaryl”, “heteroaromatic”, “heteroaryl ring”, “heteroaryl group” and “heteroaromatic group”, used alone or as part of a larger moiety as in “heteroaralkyl” refers to heteroaromatic ring groups having five to fourteen members, including monocyclic heteroaromatic rings and polycyclic aromatic rings in which a monocyclic aromatic ring is fused to one or more other aromatic ring (carbocyclic or heterocyclic). Heteroaryl groups have one or more ring heteroatoms. Examples of heteroaryl groups include 2-furanyl, 3-furanyl, N-imidazolyl, 2-imidazolyl, 4-imidazolyl, 5-imidazolyl, 3-isoxazolyl, 4-isoxazolyl, 5-isoxazolyl, oxadiazolyl, oxadiazolyl, 2-oxazolyl, 4-oxazolyl, 5-oxazolyl, N-pyrazolyl, 3-pyrazolyl, 4-pyrazolyl, 5-pyrazolyl, N-pyrrolyl, 2-pyrrolyl, 3-pyrrolyl, 2-pyridyl, 3-pyridyl, 4-pyridyl, 2-pyrimidinyl, 4-pyrimidinyl, 5-pyrimidinyl, 3-pyridazinyl, 4-pyridazinyl, 2-thiazolyl, 4-thiazolyl, 5-thiazolyl, triazolyl, tetrazolyl, 2-thienyl, 3-thienyl, carbazolyl, benzothienyl, benzofuranyl, indolyl, quinolinyl, benzothiazole, benzooxazole, benzimidazolyl, isoquinolinyl and isoindolyl. Also included within the scope of the term “heteroaryl”, as it is used herein, is a group in which an aromatic ring is fused to one or more non-aromatic rings (carbocyclic or heterocyclic).

An “arylene” group as defined herein is a bivalent group represented by —Ar—, wherein Ar is an aromatic group as defined above.

The term non-aromatic heterocyclic group used alone or as part of a larger moiety refers to non-aromatic heterocyclic ring groups having three to fourteen members, including monocyclic heterocyclic rings and polycyclic rings in which a monocyclic ring is fused to one or more other non-aromatic carbocyclic or heterocyclic ring or aromatic ring (carbocyclic or heterocyclic). Heterocyclic groups have one or more ring heteroatoms, and can be saturated or contain one or more units of unsaturation. Examples of heterocyclic groups include piperidinyl, piperizinyl, pyrrolidinyl, pyrazolidinyl, imidazolidinyl, tetrahydroquinolinyl, inodolinyl, isoindolinyl, tetrahydrofuranyl, oxazolidinyl, thiazolidinyl, dioxolanyl, dithiolanyl, tetrahydropyranyl, dihydropyranyl, azepanyl and azetidinyl

The term “heteroatom” means nitrogen, oxygen, or sulfur and includes any oxidized form of nitrogen and sulfur, and the quaternized form of any basic nitrogen. Also the term “nitrogen” includes a substitutable nitrogen of a heteroaryl or non-aromatic heterocyclic group. As an example, in a saturated or partially unsaturated ring having 0-3 heteroatoms selected from oxygen, sulfur or nitrogen, the nitrogen may be N (as in 3,4-dihydro-2H-pyrrolyl), NH (as in pyrrolidinyl) or NR′ (as in N-substituted pyrrolidinyl), wherein R′ is a suitable substituent for the nitrogen atom in the ring of a non-aromatic nitrogen-containing heterocyclic group, as defined below. Preferably the nitrogen is unsubstituted.

As used herein the term non-aromatic carbocyclic ring as used alone or as part of a larger moiety refers to a non-aromatic carbon containing ring which can be saturated or contain one or more units of unsaturation, having three to fourteen atoms including monocyclic and polycyclic rings in which the carbocyclic ring can be fused to one or more non-aromatic carbocyclic or heterocyclic rings or one or more aromatic (carbocyclic or heterocyclic) rings

An optionally substituted aryl group as defined herein may contain one or more substitutable ring atoms, such as carbon or nitrogen ring atoms. Examples of suitable substituents on a substitutable ring carbon atom of an aryl group include halogen (e.g., —Br, Cl, I and F), —OH, C1-C4 alkyl, C1-C4 haloalkyl, —NO2, C1-C4 alkoxy, C1-C4 haloalkoxy, —CN, —NH2, C1-C4 alkylamino, C1-C4 dialkylamino, —C(O)NH2, —C(O)NH(C1-C4 alkyl), —C(O)(C1-C4 alkyl), —OC(O)(C1-C4 alkyl), —OC(O)(aryl), —OC(O)(substituted aryl), —OC(O)(aralkyl), —OC(O)(substituted aralkyl), —NHC(O)H, —NHC(O)(C1-C4 alkyl), —C(O)N(C1-C4 alkyl)2, —NHC(O)O—(C1-C4 alkyl), —C(O)OH, —C(O)O—(C1-C4 alkyl), —NHC(O)NH2, —NHC(O)NH(C1-C4 alkyl), —NHC(O)N(C1-C4 alkyl)2, —NH—C(═NH)NH2, —SO2NH2—SO2NH(C1-C3alkyl), —SO2N(C1-C3alkyl)2, NHSO2H, NHSO2(C1-C4 alkyl) and aryl. Preferred substituents on aryl groups are as defined throughout the specification. In certain embodiments aryl groups are unsubstituted.

Examples of suitable substituents on a substitutable ring nitrogen atom of an aryl group include C1-C4 alkyl, NH2, C1-C4 alkylamino, C1-C4 dialkylamino, —C(O)NH2, —C(O)NH(C1-C4 alkyl), —C(O)(C1-C4 alkyl), —CO2R**, —C(O)C(O)R**, —C(O)CH3, —C(O)OH, —C(O)O—(C1-C4 alkyl), —SO2NH2—SO2NH(C1-C3alkyl), —SO2N(C1-C3alkyl)2, NHSO2H, NHSO2(C1-C4 alkyl), —C(═S)NH2, —C(═S)NH(C1-C4 alkyl), —C(═S)N(C1-C4 alkyl)2, —C(═NH)—N(H)2, —C(═NH)—NH(C1-C4 alkyl) and —C(═NH)—N(C1-C4 alkyl)2,

An optionally substituted alkyl group or non-aromatic carbocyclic or heterocyclic group as defined herein may contain one or more substituents. Examples of suitable substituents for an alkyl group include those listed above for a substitutable carbon of an aryl and the following: ═O, ═S, ═NNHR**, ═NN(R**)2, ═NNHC(O)R**, ═NNHCO2 (alkyl), ═NNHSO2 (alkyl), ═NR**, spiro cycloalkyl group or fused cycloalkyl group. R** in each occurrence, independently is —H or C1-C6 alkyl. Preferred substituents on alkyl groups are as defined throughout the specification. In certain embodiments optionally substituted alkyl groups are unsubstituted.

A “spiro cycloalkyl” group is a cycloalkyl group which shares one ring carbon atom with a carbon atom in an alkylene group or alkyl group, wherein the carbon atom being shared in the alkyl group is not a terminal carbon atom.

In yet another embodiment, the present invention is a method of producing a compound herein using methods known in the art of organic and polymer chemistry.

In certain embodiments, this invention can allow synthesizing the antioxidants described herein cost effectively.

In various embodiments, the antioxidants of the present invention can be prepared by the modification of compounds represented by the following Structural Formula:


wherein X is —C(O)OH, —OH, —NRC2 or —SH and the remainder of the variables are as described above.

In various embodiments, the antioxidants of the present invention can be prepared by coupling of the compounds represented by the following Structural Formula:


wherein the variables are as described above.

In various embodiments, intermediates in the compounds of the present invention can be prepared by methods described in U.S. Publication Nos.: 2006/0041094 and 2006/0041087 U.S. application Ser. Nos. 11/292,813, 11/293,050, 11/293,049 and 11/293,844, 11/389,564, the entire teachings of each of these references are incorporated herein by reference

In certain embodiments the antioxidants of the present invention can have significantly higher antioxidant activities along with improved thermal stability and performance in a wide range of materials including but not limited to plastics, elastomers, lubricants, petroleum based products (lubricants, gasoline, aviation fuels, and engine oils), cooking oil, cosmetics, processed food products, compared to commercially available antioxidants. In general, the antioxidants of the Structural Formulas I, II, and III have superior performance in materials including but not limited to polyolefins.

The compounds of the present invention can be used as antioxidants to inhibit oxidation of an oxidizable material. Such as, for example to increase the shelf life of an oxidizable material.

The antioxidant compounds of the present invention can be employed to inhibit the oxidation of an oxidizable material, for example by contacting the material with an antioxidant compound of the present invention.

For purposes of the present invention, a method of “inhibiting oxidation” is a method that inhibits the propagation of a free radical-mediated process. Free radicals can be generated by heat, light, ionizing radiation, metal ions and some proteins and enzymes. Inhibiting oxidation also includes inhibiting reactions caused by the presence of oxygen, ozone or another compound capable of generating these gases or reactive equivalents of these gases.

As used herein the term “oxidizable material” is any material which is subject to oxidation by free-radicals or oxidative reaction caused by the presence of oxygen, ozone or another compound capable of generating these gases or reactive equivalents thereof.

In certain embodiments, the oxidizable material is an organic polymer or plastic. In certain embodiments, the oxidizable material is an elastomer. In certain embodiments, the oxidizable material is a lubricant. In certain embodiments, the oxidizable material is a petroleum based product. In certain embodiments, the oxidizable material is an edible oil or cooking oil. In certain embodiments, the oxidizable material is a cosmetic. In certain embodiments, the oxidizable material is a processed food product.

In particular the oxidizable material is a lubricant or a mixture of lubricants.

The shelf life of many materials and substances contained within the materials, such as packaging materials, are enhanced by the presence of the antioxidants of the present invention. The addition of an antioxidant of the present invention to a packaging material is believed to provide additional protection to the product contained inside the package. In addition, the properties of many packaging materials themselves, particularly polymers, are enhanced by the presence of an antioxidant regardless of the application (i.e., not limited to use in packaging). Common examples of packaging materials include paper, cardboard and various plastics and polymers. A packaging material can be coated with an antioxidant (e.g., by spraying the antioxidant or by applying as a thin film coating), blended with or mixed with an antioxidant, or otherwise have an antioxidant present within it. In one example, a thermoplastic such as polyethylene, polypropylene or polystyrene can be melted in the presence of an antioxidant in order to minimize its degradation during the polymer processing.

The lifetime of lubricants, lubricant oils, mixtures thereof and compositions comprising lubricants and lubricant oils in general can be improved by contacting the lubricant, lubricant oil, mixtures thereof or composition comprising the lubricant or lubricant oil or mixtures thereof with compounds of the present invention, as described herein.

In certain embodiments of the present invention, polyolefins and mixtures of polyolefins can be stabilized by contacting the polyolefin or mixture of polyolefins with a compound of the present invention. These polyolefins and mixtures of polyolefins, include, but are not limited to substituted polyolefins, polyacrylates, polymethacrylates and copolymers of polyolefins. The following are examples of some types of polyolefins which can be stabilized by the methods of the present invention:

1. Polymers of monoolefins and diolefins, for example polypropylene, polyisobutylene, polybut-1-ene, poly-4-methylpent-1-ene, polyisoprene or polybutadiene, as well as polymers of cycloolefins, for instance of cyclopentene or norbornene, polyethylene (which optionally can be crosslinked), for example high density polyethylene (HDPE), high density and high molecular weight polyethylene (HDPE-HMW), high density and ultrahigh molecular weight polyethylene (HDPE-UHMW), medium density polyethylene (MDPE), low density polyethylene (LDPE), linear low density polyethylene (LLDPE), very low density polyethylene (VLDPE) and ultra low density polyethylene (ULDPE).

Polyolefins, i.e. the polymers of monoolefins exemplified in the preceding paragraph, for example polyethylene and polypropylene, can be prepared by different, and especially by the following, methods:

i) radical polymerization (normally under high pressure and at elevated temperature).

ii) catalytic polymerization using a catalyst that normally contains one or more than one metal of groups IVb, Vb, VIb or VIII of the Periodic Table. These metals usually have one or more than one ligand, typically oxides, halides, alcoholates, esters, ethers, amines, alkyls, alkenyls and/or aryls that may be either p- or s-coordinated. These metal complexes may be in the free form or fixed on substrates, typically on activated magnesium chloride, titanium(III) chloride, alumina or silicon oxide. These catalysts may be soluble or insoluble in the polymerization medium. The catalysts can be used by themselves in the polymerization or further activators may be used, typically metal alkyls, metal hydrides, metal alkyl halides, metal alkyl oxides or metal alkyloxanes, said metals being elements of groups Ia, Ia and/or IIIa of the Periodic Table. The activators may be modified conveniently with further ester, ether, amine or silyl ether groups. These catalyst systems are usually termed Phillips, Standard Oil Indiana, Ziegler (-Natta), TNZ (DuPont), metallocene or single site catalysts (SSC).

2. Mixtures of the polymers mentioned under 1., for example, mixtures of polypropylene with polyisobutylene, polypropylene with polyethylene (for example PP/HDPE, PP/LDPE) and mixtures of different types of polyethylene (for example LDPE/HDPE).

3. Copolymers of monoolefins and diolefins with each other or with other vinyl monomers, for example ethylene/propylene copolymers, linear low density polyethylene (LLDPE) and mixtures thereof with low density polyethylene (LDPE), propylene/but-1-ene copolymers, propylene/isobutylene copolymers, ethylene/but-1-ene copolymers, ethylene/hexene copolymers, ethylene/methylpentene copolymers, ethylene/heptene copolymers, ethylene/octene copolymers, propylene/butadiene copolymers, isobutylene/isoprene copolymers, ethylene/alkyl acrylate copolymers, ethylene/alkyl methacrylate copolymers, ethylene/vinyl acetate copolymers and their copolymers with carbon monoxide or ethylene/acrylic acid copolymers and their salts (ionomers) as well as terpolymers of ethylene with propylene and a diene such as hexadiene, dicyclopentadiene or ethylidene-norbornene; and mixtures of such copolymers with one another and with polymers mentioned in 1) above, for example polypropylene/ethylene-propylene copolymers, LDPE/ethylene-vinyl acetate copolymers (EVA), LDPE/ethylene-acrylic acid copolymers (EAA), LLDPE/EVA, LLDPE/EAA and alternating or random polyalkylene/carbon monoxide copolymers and mixtures thereof with other polymers, for example polyamides.

4. Blends of polymers mentioned under 1. with impact modifiers such as ethylene-propylene-diene monomer copolymers (EPDM), copolymers of ethylene with higher alpha-olefins (such as ethylene-octene copolymers), polybutadiene, polyisoprene, styrene-butadiene copolymers, hydrogenated styrene-butadiene copolymers, styrene-isoprene copolymers, hydrogenated styrene-isoprene copolymers. These blends are commonly referred to in the industry as TPO's (thermoplastic polyolefins).

In certain particular embodiments polyolefins of the present invention are for example polypropylene homo- and copolymers and polyethylene homo- and copolymers. For instance, polypropylene, high density polyethylene (HDPE), linear low density polyethylene (LLDPE) and polypropylene random and impact (heterophasic) copolymers.

In certain embodiments of the present invention, 50% to 20% by weight of the antioxidants of the present invention are added to the polyolefin. In certain other embodiments of the present invention, 10% to 5% by weight of the antioxidants of the present invention are added to the polyolefin. In certain other embodiments of the present invention, 0.1% to 2% by weight of the antioxidants of the present invention are added to the polyolefin. In certain other embodiments of the present invention, 0.001% to 0.5% by weight of the antioxidants of the present invention are added to the polyolefin. This percentage varies depending upon their end application and type of the polyolefin.

In certain embodiments of the present invention the antioxidants of the present invention are usually added to the polyolefin with stirring at between 0 and 100° C., between 10 and 80° C., between 20-30° C. or at room temperature.

In certain embodiments the antioxidants of the present invention can be mixed with other antioxidants or additives to produce formulations, such as those described in Provisional Patent Application No. 60/742,150, filed Dec. 2, 2005, Title: Lubricant Composition, by Kumar, Rajesh, et al., and Provisional Patent Application No. 60/731,325, filed Oct. 27, 2005, Title: Stabilized Polyolefin Composition, by Kumar, Rajesh, et al., the entire contents of each of which are incorporated herein by reference.

EXEMPLIFICATION Example 1 Preparation of Compound A

In a 1 L 3-necked flask, equipped with a stirrer, and a Dean-Starke water trap carrying a reflux condenser, was charged 21.6 g (0.1 mole) of 3,3′-dihydroxybenzidine, 55.6 g (0.2 mole) of 3,5-di-tert-butyl-4-hydroxyphenylpropionic acid, 1.22 g (0.02 mole) of powdered boric acid, 500 ml of toluene and 50 ml of dimethyl sulfoxide. Reactants were heated at 140° C. for 48 h with removal of water. At the end of the reaction, toluene was distilled off under reduced pressure and the residual melt was added to 1 lit. of water and stirred for 6 h. Solids were separated by filtration. Crude solids obtained were dissolved in 500 ml acetone and to this solution was added 10 ml conc. hydrochloric acid. This acidified solution was slowly dropped with stirring in 2 lit. of water and the solids separated out collected by filtration and washed with water until the filtrate showed neutral pH. These solids were further purified by dissolving in 500 ml of methanol and treating with 3.5 g of activated charcoal at ambient temperature for 30 min. The solution was filtered and the filtrate was then added to 1 lit. of aqueous 10% sodium bicarbonate solution with vigorous stirring. Solids were collected by vacuum filtration and washed with water until the filtrate showed neutral pH. The solids were dried in vacuum at 50° C. There was obtained 63 g (85.5%) of (I) as off white powder.

Example 2 Improved Oxidation Induction Times of the Antioxidants Compound A

Compound A was evaluated and found to have desirable antioxidant properties. The antioxidant properties of this novel compound were studied by mixing 1000 ppm of compound A in polypropylene with triphosphite secondary antioxidant (1000 ppm) and CaStereate as acid scavenger. The oxidation induction time (OIT) was determined using ASTM D3895 method by differential scanning calorimetry (DSC). As shown in FIG. 1, compound A has an oxidation induction time of 85 min.

The entire contents of each of the following are incorporated herein by reference.

  • Provisional Patent Application No. 60/632,893, filed Dec. 3, 2004, Title: Process For The Synthesis Of Polyalkylphenol Antioxidants, by Suizhou Yang, et al;
  • Patent application Ser. No. 11/292,813 filed Dec. 2, 2005, Title: Process For The Synthesis Of Polyalkylphenol Antioxidants, by Suizhou Yang, et al;
  • Provisional Patent Application No. 60/633,197, filed Dec. 3, 2004, Title: Synthesis Of Sterically Hindered Phenol Based Macromolecular Antioxidants, by Ashish Dhawan, et al.;
  • Patent application Ser. No. 11/293,050; filed Dec. 2, 2005, Title: Synthesis Of Sterically Hindered Phenol Based Macromolecular Antioxidants, by Ashish Dhawan, et al.;
  • Provisional Patent Application No. 60/633,252, filed Dec. 3, 2004, Title: One Pot Process For Making Polymeric Antioxidants, by Vijayendra Kumar, et al.;
  • Patent application Ser. No. 11/293,049; filed Dec. 2, 2005, Title: One Pot Process For Making Polymeric Antioxidants, by Vijayendra Kumar, et al.;
  • Provisional Patent Application No. 60/633,196, filed Dec. 3, 2004, Title: Synthesis Of Aniline And Phenol-Based Macromonomers And Corresponding Polymers, by Rajesh Kumar, et al.;
  • Patent application Ser. No. 11/293,844; filed Dec. 2, 2005, Title: Synthesis Of Aniline And Phenol-Based Macromonomers And Corresponding Polymers, by Rajesh Kumar, et al.;
  • Patent application Ser. No. 11/184,724, filed Jul. 19, 2005, Title: Anti-Oxidant Macromonomers And Polymers And Methods Of Making And Using The Same, by Ashok L. Cholli;
  • Patent application Ser. No. 11/184,716, filed Jul. 19, 2005, Title: Anti-Oxidant Macromonomers And Polymers And Methods Of Making And Using The Same, by Ashok L. Cholli;
  • Patent application Ser. No. 11/360,020, filed Feb. 22, 2006, Title: Nitrogen And Hindered Phenol Containing Dual Functional Macromolecules: Synthesis And Their Antioxidant Performances In Organic Materials, by Rajesh Kumar, et al.
  • Provisional Patent Application No. 60/655,169, filed Mar. 25, 2005, Title: Alkylated Macromolecular Antioxidants And Methods Of Making, And Using The Same, by Rajesh Kumar, et al.
  • Provisional Patent Application No. 60/731,125, filed Oct. 27, 2005, Title: Macromolecular Antioxidants And Polymeric Macromolecular Antioxidants, by Ashok L. Cholli, et al.
  • Provisional Patent Application No. 60/731,021, filed Oct. 27, 2005, Title: Macromolecular Antioxidants Based On Sterically Hindered Phenols And Phosphites, by Ashok L. Cholli, et al.
  • Provisional Patent Application No. 60/742,150, filed Dec. 2, 2005, Title: Lubricant Composition, by Kumar, Rajesh, et al.
  • Provisional Patent Application No. 60/731,325, filed Oct. 27, 2005, Title: Stabilized Polyolefin Composition, by Kumar, Rajesh, et al.
  • Patent application Ser. No. 11/040,193, filed Jan. 21, 2005, Title: Post-Coupling Synthetic Approach For Polymeric Antioxidants, by Ashok L. Choll, et al.;
  • Patent Application No. PCT/US2005/001948, filed Jan. 21, 2005, Title: Post-Coupling Synthetic Approach For Polymeric Antioxidants, by Ashok L. Cholli et al.;
  • Patent Application No. PCT/US2005/001946, filed Jan. 21, 2005, Title: Polymeric Antioxidants, by Ashok L. Choll, et al.;
  • Patent Application No. PCT/US03/10782, filed Apr. 4, 2003, Title: Polymeric Antioxidants, by Ashok L. Choll, et al.;
  • Patent application Ser. No. 10/761,933, filed Jan. 21, 2004, Title: Polymeric Antioxidants, by Ashish Dhawan, et al.;
  • Patent application Ser. No. 10/408,679, filed Apr. 4, 2003, Title: Polymeric Antioxidants, by Ashok L. Choll, et al.;
  • U.S. Pat. No. 6,770,785 B1
  • U.S. Pat. No. 5,834,544
  • Neftekhimiya (1981), 21(2): 287-298.

While this invention has been particularly shown and described with references to preferred embodiments thereof, it will be understood by those skilled in the art that various changes in form and details may be made therein without departing from the scope of the invention.

EQUIVALENTS

Those skilled in the art will recognize, or be able to ascertain using no more than routine experimentation, many equivalents to specific embodiments of the invention described specifically herein. Such equivalents are intended to be encompassed in the scope of the following claims.

Patent Citations
Cited PatentFiling datePublication dateApplicantTitle
US3294836Sep 17, 1962Dec 27, 1966Geigy Chem CorpStabilization of organic material with certain esters of substituted hydroquinones and organic acids
US3441545Nov 1, 1963Apr 29, 1969Du PontModification of olefin-carboxylic acid halide copolymers
US3459704Oct 31, 1966Aug 5, 1969Geigy Chem CorpCompositions of organic material stabilized with certain esters of substituted hydroquinones and organic acids
US3557245Sep 11, 1967Jan 19, 1971Technology UkPolymeric antioxidants for elastomers and rubbers
US3632785Feb 19, 1969Jan 4, 1972Georgia Pacific CorpMethod of forming shell molds
US3645970Oct 1, 1969Feb 29, 1972Ciba Geigy CorpBenzoate homopolymers hindered phenolic groups as stabilizers
US3649667Jun 24, 1970Mar 14, 1972American Cyanamid CoAryl polyesters of 3 5-dialkyl-4-hydroxy-phenyl-alkanoic acids
US3655831Sep 11, 1969Apr 11, 1972Weston Chemical CorpPentaerythritol diphosphites
US3870680Oct 19, 1973Mar 11, 1975Edward SchurdakCopper inhibitors for polyolefins
US3907939Jun 16, 1969Sep 23, 1975Ashland Oil IncPhosphite esters of hindered phenols
US3953402Jul 20, 1970Apr 27, 1976The Goodyear Tire & Rubber CompanyAge resistant polymers of ditertiary alkyl-4-hydroxyaryl acrylate and dienes
US3965039Nov 19, 1974Jun 22, 1976Chaplits Donat NIon-exchange molded catalyst and method of its preparation
US3983091Jul 25, 1975Sep 28, 1976The Goodyear Tire & Rubber CompanyPhenolic antioxidants prepared from tricyclopentadiene and stabilized compositions
US3996160Feb 24, 1975Dec 7, 1976Dynapol CorporationHydroquinonoid ortho-alkylation polymers and the process of their production
US3996198Feb 24, 1975Dec 7, 1976DynapolOne step preparation of linear antioxidant phenolic polymers involving use of impure diolefin feedstock and aluminum catalyst under ortho alkylation conditions
US4054676Dec 4, 1974Oct 18, 1977DynapolEdible with polymeric hydroquinone antioxidant
US4094857Sep 1, 1977Jun 13, 1978E. I. Du Pont De Nemours And CompanyCopolymerizable phenolic antioxidant
US4096319Dec 11, 1975Jun 20, 1978Rohm And Haas CompanyOil additives for diesel engine lubricants
US4097464Nov 3, 1975Jun 27, 1978The Goodyear Tire & Rubber Company2,6-Di-tert-alkyl-4-vinylphenols as polymerizable antioxidants
US4098829May 19, 1977Jul 4, 1978DynapolPolymeric hydroquinone antioxidant
US4107144Apr 15, 1977Aug 15, 1978Canadian Patents And Development LimitedPhenolic antioxidants with polymer tails
US4136055Aug 23, 1976Jan 23, 1979Raychem CorporationRepeating hindered bisphenolic units, for incorporation in olefin polymers
US4202816Nov 7, 1977May 13, 1980Ciba-Geigy CorporationEnol-piperidine metal complexes
US4205151Aug 2, 1977May 27, 1980DynapolPolymeric N-substituted maleimide antioxidants
US4213892Mar 5, 1975Jul 22, 1980Gerald ScottProcess for preparing oxidatively-stable polymers by reaction with antioxidant in the presence of free radical
US4219453Sep 15, 1978Aug 26, 1980Asahi Kasei Kogyo Kabushiki KaishaInorganic filler-incorporated ethylene polymer film
US4267358Mar 13, 1980May 12, 1981Borg-Warner CorporationOrtho-alkyl-substituted 3-/p-hydroxyphenyl/propyl3-/p-hydroxyphenyl/propionate; stabilizers for addition polymers; heat resistance
US4281192Oct 16, 1979Jul 28, 1981L'orealN-(2,5-Dihydroxy-3,4,6-trimethyl-benzyl)-acrylamide and-methacrylamide
US4283572Dec 27, 1979Aug 11, 1981Borg-Warner CorporationIn the presence of a dehydrated sulfonated ion exchange resin
US4317933Nov 9, 1977Mar 2, 1982The Goodyear Tire & Rubber CompanyAlkylating to produce an aldehyde substituted phenol, esters thereof
US4341879Mar 11, 1981Jul 27, 1982Mitsubishi Gas Chemical Company, Inc.Polyphenylene ether resin composition having improved heat stability and impact strength
US4355148Sep 18, 1980Oct 19, 1982The B. F. Goodrich CompanyPolyalkenamers
US4377666Aug 17, 1981Mar 22, 1983Phillips Petroleum CompanyAge-resistant polymers containing chemically bound antioxidant functional groups
US4380554Jul 21, 1981Apr 19, 1983Standard Oil Company (Indiana)Stabilizers for edible lipids
US4447657Nov 10, 1982May 8, 1984Uop Inc.Rearrangement of alkyl phenyl ethers on alumina catalyst
US4465871Aug 8, 1983Aug 14, 1984Uop Inc.Preparation of 2-t-butyl-4-alkoxy- and 4-hydroxyphenols
US4510296May 10, 1984Apr 9, 1985The United States Of America As Represented By The Administrator Of The National Aeronautics And Space AdministrationPhenoxy resins containing pendent ethynyl groups and cured resins obtained therefrom
US4511491Jul 15, 1983Apr 16, 1985Sumitomo Chemical Co., Ltd.Stabilizers for synthetic resins
US4690995Jun 6, 1985Sep 1, 1987The Dow Chemical CompanyCopolymers containing high concentrations of phenol antioxidant units
US4761247Mar 6, 1987Aug 2, 1988Morton Thiokol, Inc.Phenol-stabilized microbiocidal compositions
US4824929Sep 8, 1987Apr 25, 1989Toyo Boseki Kabushiki KaishaPolymeric antioxidant and process for production thereof
US4849503Dec 21, 1987Jul 18, 1989Amoco CorporationNovel poly(aryl ethers)
US4855345Jun 10, 1987Aug 8, 1989Ciba-Geigy CorporationBis/p-hydroxybenzyl/phenyl phosphites
US4857596Aug 12, 1987Aug 15, 1989Pennwalt CorporationPolymer bound antioxidant stabilizers
US4870214May 20, 1988Sep 26, 1989Ethyl CorporationOlefin homo- and copolymers
US4894263Oct 24, 1988Jan 16, 1990Thomson-CsfMesomorphic polymer material usable in non linear optics
US4897438Feb 25, 1988Jan 30, 1990Hitachi Chemical Company, Ltd.Stabilized synthetic resin composition
US4900671Jul 8, 1987Feb 13, 1990The Mead CorporationBiocatalytic process for preparing phenolic resins using peroxidase or oxidase enzyme
US4925591Dec 22, 1988May 15, 1990Mitsubishi Rayon Co., Ltd.Mesomorphic compound having β-hydroxycarboxyl group as chiral source and liquid crystal composition
US4968759Feb 23, 1988Nov 6, 1990Hitachi Chemical Company, Ltd.Alkylation polymerization of phenol with bis(hydroxyalkyl)benzene followed by alkylation of ortho or para position
US4977004Oct 19, 1988Dec 11, 1990Tropicana Products, Inc.Multilayer; ethylene-vinyl alcohol copolymer
US4981917Jun 22, 1989Jan 1, 1991Atochem North America, Inc.Anhydride or diacid polymers crosslinked with hydrazide-type agent
US4994628Sep 25, 1989Feb 19, 1991Ethyl Corporation3,5-Dialkyl-4-hydroxybenzyl-substituted benzenes by reacting 2,6-dialkyl-4-methoxymethyl phenols with benzene compound; sulfuric acid catalyst
US5013470Oct 10, 1989May 7, 1991Texaco Inc.Antioxidant VII lubricant additive
US5017727Jul 10, 1990May 21, 1991Copolymer Rubber & Chemical CorporationNorbornene derivatives
US5082358Jun 22, 1989Jan 21, 1992Canon Kabushiki KaishaPolymer of vinyl-biphenyl derivative adapted for optical use
US5102962Mar 27, 1990Apr 7, 1992Hitachi Chemical Company, Ltd.Phenolic polymer and production thereof
US5117063Jun 21, 1991May 26, 1992Monsanto CompanyMethod of preparing 4-aminodiphenylamine
US5143828Dec 31, 1991Sep 1, 1992The United States Of America As Represented By The Secretary Of The ArmyLangmuir-blodgett process
US5185391Nov 27, 1991Feb 9, 1993The Dow Chemical CompanyAromatic secondary amines, hydroxyphenylalkylesters as antioxidants; heat and chemical resistant, dielectrics
US5185407Aug 29, 1991Feb 9, 1993Shell Oil CompanyPolymeric phenolic esters
US5188953May 22, 1991Feb 23, 1993The Mead CorporationBiocatalytic oxidation using soybean peroxidase
US5191008Oct 21, 1991Mar 2, 1993The Goodyear Tire & Rubber CompanyProcess for the production of latexes by the selective monomer addition
US5196142Aug 2, 1991Mar 23, 1993Ciba-Geigy CorporationFor stabilizing emulsion polymerized polymers
US5206303Dec 27, 1990Apr 27, 1993Exxon Chemical Patents Inc.Entanglement-inhibited macromolecules
US5207939Aug 23, 1990May 4, 1993Mobil Oil CorporationLubricants with oxidation resistance
US5274060Feb 27, 1992Dec 28, 1993Ciba-Geigy CorporationMonomers of ether-substituted styrene derivatives
US5278055Jun 9, 1992Jan 11, 1994The Mead CorporationBiocatalytic production of phenolic resins with ramped peroxide addition
US5304589Jan 18, 1991Apr 19, 1994Bp Chemicals LimitedReacting an olefin polymer and a dicyclopentadiene polymer modified by a phenol in the melt phase and with a free radical catalyst; molding materials
US5320889Oct 21, 1991Jun 14, 1994Tropicana Products, Inc.Plastic bottle for food
US5449715Jul 15, 1993Sep 12, 1995Isp Investments Inc.Colorless, non-toxic, stabilized aqueous solution of a C1-C5 alkyl vinyl ether and maleic acid copolymers
US5498809May 22, 1995Mar 12, 1996Exxon Chemical Patents Inc.Terminal ethylvinylidene groups which can be functionalized, dispersants
US5516856Jan 18, 1995May 14, 1996Elf Atochem North America, Inc.Process for the use of antioxidant-peroxides to cure and enhance the stability of polymers
US5541091Apr 5, 1995Jul 30, 1996Enzymol International, Inc.Process for the biocatalytic coupling of aromatic compounds in the presence of a radical transfer agent
US5565300Jan 30, 1991Oct 15, 1996Fuji Photo Film Co., Ltd.Positive photoresist composition
US5574118Mar 6, 1995Nov 12, 1996Dsm Copolymer, Inc.Olefin polymers containing bound antioxidant
US5652201Jul 11, 1995Jul 29, 1997Ethyl Petroleum Additives Inc.Lubricating oil compositions and concentrates and the use thereof
US5739341Jun 2, 1995Apr 14, 1998Ciba Specialty Chemicals CorporationLiquid antioxidants as stabilizers
US5834544Oct 20, 1997Nov 10, 1998Uniroyal Chemical Company, Inc.Organic materials stabilized by compounds containing both amine and hindered phenol functional functionalities
US5837798Mar 18, 1997Nov 17, 1998Georgia-Pacific ResinsOil solubility; colorless
US5869592Aug 19, 1991Feb 9, 1999Maxdem IncorporatedMacromonomers having reactive side groups
US5911937Mar 5, 1996Jun 15, 1999Capitol Specialty Plastics, Inc.Packaging material having a desiccant contained therein
US5994498Aug 21, 1997Nov 30, 1999Massachusetts Lowell, University Of LowellMethod of forming water-soluble, electrically conductive and optically active polymers
US6018018Nov 21, 1997Jan 25, 2000University Of Massachusetts LowellEnzymatic template polymerization
US6046263May 19, 1998Apr 4, 2000Ciba Specialty Chemicals CorporationLiquid antioxidants as stabilizers
US6096695Jun 3, 1996Aug 1, 2000Ethyl CorporationSulfurized phenolic antioxidant composition, method of preparing same, and petroleum products containing same
US6096859Jan 16, 1996Aug 1, 2000The United States Of America As Represented By The Secretary Of The ArmyProcess to control the molecular weight and polydispersity of substituted polyphenols and polyaromatic amines by enzymatic synthesis in organic solvents, microemulsions, and biphasic systems
US6150491Nov 6, 1998Nov 21, 2000The United States Of America As Represented By The Secretary Of The ArmyPolyaromatic compounds and method for their production
US6232314May 12, 1997May 15, 2001Monash UniversityArylalkylpiperazine compounds as antioxidants
US6342549Jan 5, 1996Jan 29, 2002Mitsui Chemicals, Inc.Cycloolefin resin pellets and a process for producing a molded product thereof
US6444450Jan 28, 1998Sep 3, 2002The United States Of America As Represented By The Secretary Of The ArmyLarge-scale production of polyphenols or polyaromatic amines using enzyme-mediated reactions
US6646035Feb 21, 2001Nov 11, 2003Clariant Finance (Bvi) LimitedA stabilizer for thermoplastic polymers comprising bis(3,3-(4'-hydroxy)-3'-tert-butyl-phenyl)-butanoic acid)-glycol-ester and at least one other phenolic antioxidant; water pipes; waterproofing; water storage;
US6723815May 13, 2003Apr 20, 2004Alcon, Inc.Intraocular lenses and contact lenses; hydrophobic aryl acrylic monomer, a hydrophilic monomer selected from hydroxyalkyl (meth)acrylates, n-vinyl pyrrolidone and acrylamides, and a reactive plasticizer
US6743525Feb 22, 2001Jun 1, 2004Koninklijke Philips Electronics N.V.Electroluminescent device
US6770785Mar 25, 2003Aug 3, 2004Council Of Scientific And Industrial ResearchAntiozonant cum antioxidant, process for preparation
US6794480Mar 26, 2002Sep 21, 2004Jsr CorporationPolyarylene-based copolymer useful as proton-conductive membrane which can be used as electron for primary battery, electrolyte for secondary battery, high molecular solid electrolyte for fuel cell
US6800228Mar 20, 2000Oct 5, 2004Albemarle CorporationSterically hindered phenol antioxidant granules having balanced hardness
US6828364Jul 5, 2001Dec 7, 2004Ciba Specialty Chemicals CorporationStabilizer mixtures
USRE35247Jul 5, 1994May 21, 1996The Mead CorporationBiocatalytic production of phenolic resins with ramped peroxide addition
Non-Patent Citations
Reference
1Akkara, J.A., et al., "Hematin-Catalyzed Polymerization of Phenol Compounds," Macromolecules, 33(7):2377-2382 (2000).
2Akkara, J.A., et al., "Synthesis and Characterization of Polymers Produced by Horseradish Peroxidase in Dioxane," J. of Polymer Science: Part A: Polymer Chemistry, 29(11):1561-1574 (1991).
3Armengol, E., et al., "Acid Zeolites as Catalysts in Organic Reactions, tert-Butylation of Anthracene, Naphthalene and Thianthrene," Appl. Catal. A 149:411-423 (1997).
4Ayyagari, M.S., et al., "Controlled Free-Radical Polymerization of Phenol Derivatives by Enzyme-Catalyzed Reactions in Organic Solvents," Macromolecules, 28(15):5192-5197 (1995).
5Badamali, S.K., et al., "Influence of Aluminium Sources on the Synthesis and Catalytic Activity of Mesoporous AIMCM-41 Molecular Sieves," Catal. Today 63:291-295 (2000).
6Belyaev, A., et al., "Structure-Activity Relationship of Diaryl Phosphonate Esters as Potent Irreversible Dipeptidyl Peptidase IV Inhibitors," J. Med. Chem., 42(6):1041-1052 (1998).
7Blokhin, Y.I, et al., "Phosphorylation of Dihydric Phenols with Amides of Phosphorous Acid," Russian Chem. Bulletin, 45(9):2250-2251 (1996).
8Bruno, F.F., et al., "Enzymatic Template Synthesis of Polyphenol," Materials Research Society Symposium Proceedings vol. 600, Electroactive Polymers (EAP):255-259 (1999).
9Chandra, K.G. and Sharma, M.M., "Alkylation of Phenol with MTBE and Other tert-butylethers:Cation Exchange Resins as Catalysts," Catal. Lett. 19(4):309-317 (1993).
10Circ-Marjanovic, et al., Chemical Oxidative Polymerization of Aminodiphenylamines, Journal of Physical Chemistry B, 112, 23: 6976-6987 (2008).
11Coppinger, G.B., et al., "Photo-Fries Rearrangement of Aromatic Esters. Role of Steric and Electronic Factors" J. of Phy. Chem., 70(11):3479-3489 (1966).
12Database CA [online] Chemical Abstracts Service, Columbus, Ohio, US, XP-002429584, Database Accession No. 81::153647, Organic Phosphate Stabilizers for Polyamides and Polyurethanes, abstract, Minagawa, M. (1974).
13Database Caplus [online] Chemical Abstracts Service, Columbus, Ohio, US, XP-002387095, Database Accession No. 1981:572206, Effectiveness of Inhibitors in the Oxidation of Jet Fuel with an Initiator, abstract, Kovalev, et al.
14Devassy, B.M., et al., "Zirconia Supported Phosphotungstic Acid as an Efficient Catalyst for Resorcinol tert-Butylation and n-Heptane Hydroisomerization," J. Mol. Catalysis A: Chemical 221:113-119 (2004).
15Ding, et al., "Chemical Trapping Experiments Support a Cation-Radical Mechanism for the Oxidative Polymerization of Aniline," Journal of Polymer Science, Part A: Polymer Chemistry, vol. 37: 2569-2579 (1999).
16Dordick, J.S., "Enzymatic Catalysis in Monophasic Organic Dolvents," Enzyme Microb. Technol., 11(4):194-211 (1989).
17Dordick, J.S., et al., "Polymerization of Phenols Catalyzed by Peroxidase in Nonaqueous Media," Biotechnology and Bioengineering, 30(1):31-36 (1987).
18English Abstract of Kovalev, G. I., et al., "Study of the Effectiveness of Inhibitors in Oxidation of Jet Fuel in a Closed Volume, " Deposited Doc., VINITI: 443-82 (1981).
19English Abstract of Kovalev, G.I., et al., "Effectiveness of Inhibitors in the Oxidation of Jet Fuel With an Initiator," J. Neftekhimiya (Petroleum Chemistry), 21(2): 287-298 (1981).
20Faber, K., "Biotransformations in Organic Chemistry," A Textbook, Fourth Completely Revised and Extended Edition, Springer-Verlag pp: 347-349 (1953).
21FS&T 821 "Antioxidant," [online], [retrieved on Oct. 29, 2002]. Retrieved from the Internet .
22FS&T 821 "Food Lipids," [online], Oct. 2001 [retrieved on Oct. 29, 2002]. Retrieved from the Internet .
23FS&T 821 "Antioxidant," [online], [retrieved on Oct. 29, 2002]. Retrieved from the Internet <URL: http://class.fst.ohio-state.edu/fst821/>.
24FS&T 821 "Food Lipids," [online], Oct. 2001 [retrieved on Oct. 29, 2002]. Retrieved from the Internet <URL: http://classfst.ohio-state.edu/fst82l/>.
25FST 821 "Course Schedule," [online], [retrieved on Oct. 29, 2002]. Retrieved from the Internet .
26FST 821 "Course Schedule," [online], [retrieved on Oct. 29, 2002]. Retrieved from the Internet <URL: http://class.fst.ohio-state.edu/fst821/>.
27Hatayama, K., et al., "Anti-ulcer Effect of Isoprenyl Flavonoids. III.1) Synthesis and Anti-ulcer Activity of Metabolites of 2'-Carboxymethoxly-4,4'-bis(3-methyl-2-butenyloxy)chalcone2)," Chemical & Pharmaceutical Bulletin, 33(4), 1327-1333(Apr. 1985).
28Heidekum, A., et al., "Nafion/Silica Composite Material Reveals High Catalytic Potential in Acylation Reactions," J. Catal. 188:230-232 (1999).
29Hidalgo, M.E., et al., "Antioxidant Activity of Depsides and Depsidones," Phytochemistry, 37(6):1585-1587 (1994).
30Hofer, K., et al., "[[(Anilinooxalyl)amino]phenyl] Phosphite Stabilizers for Polypropylene," Chemical Abstracts Service, ZCAPLUS, document No. 77:62780 (1972).
31Ikeda, R., et al., "Novel Synthetic Pathway to a Poly(phenylene oxide). Laccase-Catalyzed Oxidative Polymerization of Syringic Acid," Macromolecules, 29:3053-3054 (1996).
32International Search Report for related foreign application PCT/US2005/025513, mailed on Mar. 13, 2006.
33International Search Report for related foreign application PCT/US2005/025646, mailed on Mar. 13, 2006.
34International Search Report for related foreign application PCT/US2005/044019, mailed on Apr. 28, 2006.
35International Search Report for related foreign application PCT/US2005/044021, mailed on May 22, 2006.
36International Search Report for related foreign application PCT/US2005/044022, mailed on May 2, 2006.
37International Search Report for related foreign application PCT/US2005/044023, mailed on Nov. 3, 2006.
38International Search Report for related foreign application PCT/US2006/006355, mailed on Jul. 31, 2006.
39International Search Report for related foreign application PCT/US2006/010985, mailed on Dec. 19. 2006.
40International Search Report for related foreign application PCT/US2006/042235, mailed on Apr. 27, 2007.
41International Search Report for related foreign application PCT/US2006/042240, mailed on May 3, 2007.
42International Search Report for related foreign application PCT/US2006/045929, mailed on Apr. 20, 2007.
43International Search Report for related foreign application PCT/US2007/015177, mailed on Jun. 13, 2008.
44Ismail, M.N. and Wazzan, A.A., "Evaluation of New Thermal Stabilizers and Antifatigue Agents for Rubber Vulcanizates," Polymer-Plastics Tech. and Eng., 45:751-758 (2006).
45Jayaprakasha, G.K., et al., "Antioxidant Activity of Grape Seed (Vitis vinifera) Extracts on Peroxidation Models in Vitro," Food Chemistry, 73:285-290 (2001).
46Jialanella, G.and Pilrma, I., "Synthesis of Poly(vinyl alcohol-co-vinyl gallate) by the Chemical Modification of Poly(vinyl alcohol)," Polymer Bulletin 18:385-389 (1987).
47Joossens, J., et al., "Diphenyl Phosphonate Inhibitors for the Urokinase-Type Plasminogen Activator: Optimization of the P4 Position," J. Med. Chem., 49:5785-5793 (2006).
48Kamitori, Y., et al., "Silica Gel as an Effective Catalyst for the Alkylation of Phenols and Some Heterocylic Aromatic Compounds," J. Org. Chem. 49: 4161-4165 (1984).
49Kazandjian, R.Z., et al., "Enzymatic Analyses in Organic Solvents," Biotechnology and Bioengineering, XXVIII:417-421 (1986).
50Khan, K.M., et al., "An Expedient Esterification of Aromatic Carboxylic Acids Using Sodium Bromate and Sodium Hydrogen Sulfite," Tetrahedron 59(29):5549-5554 (2003).
51Kim, T. H., et al., "Melt Free-Radical Grafting of Hindered Phenol Antioxidant onto Polyethylene," J. Applied Polymer Science, 77:2968-2973 (2000).
52Klibanov, A.M., et al., "Enzymatic Removal of Toxic Phenols and Anilines from Waste Waters," J. of Applied Biochemistry, 2(5):414-421 (1980).
53Koshchii, V.A., et al. "Alkylation of Phenol by Alcohols in the Presence of Alumium Phenolate," Org. Chem. 24(7):1358-1361 (1988).
54Lalancette, J.M., et al. "Metals Intercalated in Graphite. II. The Friedel-Crafts Reactions with ALCL3-Graphite," Can. J. Chem. 52:589-591 (1974).
55Li, et al., "Novel Multifunctional Polymers from Aromatic Diamines by Oxidative Polymerizations," Chemical Reviews, vol. 102(9): pp. 2925-2943 (2002).
56Maki, M., et al., "Weather-Resistant Colored Polypropylene," Chemical Abstracts Service, ZCAPLUS, document No. 89:111364 (1978).
57March, J., Advanced Organic Chemistry, McGraw Hill Book Company, New York, pp. 251-259 (1977).
58Masada, H. and Oishi, Y., "A New Synthesis of aryl t-butyl Ethers," Chem. Letters, 57-58 (1978).
59Masada, H. et al., "A New Heterogeneous Williamson Synthesis of Ethers Using t-alkyl Substrates," The Chemical Society of Japan 3:275-282 (1996).
60Masada, H., et al., "A New Method for the Williamson Ether Synthesis Using t-alkyl Halides in Nonpolar Solvents," The Chemical Society of Japan, 2:164-166 (1995).
61Mehdipour-Ataei, S., et al., "Novel Diols Containing Ester and Amide Groups and Resulting Poly(ester amide ester)s," J. Applied Polymer Sci., 93:2699-2703 (2004), XP002420014.
62Mejias, L., et al. "New Polymers From Natural Phenols Using Horseradish or Soybean Peroxidase," Macromol. Biosci., 2:24-32 (2002).
63Ol'dekop, Yu. A., et al. "Simple Synthesis of the tert-butyl Ether of Phenol" Inst. Fiz-Org. Khim., Minsk, USSR. Zhurnal Obshchei Khimii, 50(2):475-6 (1980).
64Overgaag, M., et al., "Rearrangement of Alkyl Phenyl Ethers Over Dealuminated HY Zeolites Under Liquid-Phase Conditions," Applied Catalysis A: General, Elsevier Sci., 175(1-2):139-146 (1998).
65Pätoprstý, V., et al., "13C NMR Study of 3,9-Di(alkylphenoxy)-2,4,8,10-tetraoxa-3,9- diphosphaspiro[5.5]undecanes," Magnetic Resonance in Chem, 23(2):122-126 (1985).
66Pirozhenko, V.V., et al., "NMR Study of Topomerization of N-Aroyl-p-Benzoquinonemonoimines," Russian J. of Organic Chem., 31(11):1514-1519 (1995).
67Quaschning, V., et al., "Properties of Modified Zirconia Used as Friedel-Crafts-Acylation Catalysts," J. Catal. 177:164-174 (1998).
68 *RN 85650-63-1, 1984.
69Ryu, K., et al., "Peroxidase-Catalyzed Polymerization of Phenols," Biocatalysis in Agricultural Biotechnology, Chapter10:141-157 (1988).
70Sakthivel, A., et al., "Vapour Phase Tertiary Butylation of Phenol Over Sulfated Zirconia Catalyst," Catal. Lett., 72(3-4):225-228 (2001).
71Sartori G., et al., "Highly Selective Mono-tert-butylation of Aromatic Compounds," Chem. Ind., (London), (22):762-763 (1985).
72Scharpe, S.L., et al., "Serine Peptidase Modulators, Their Preparation, and Their Therapeutic Use," Chemical Abstracts Service, ZCAPLUS, document No. 131:223514 (1999).
73Search Report in international application PCT/US2006/042251 (Feb. 2007).
74Singh, A. and Kaplan, D. L., "Biocatalytic Route to Ascorbic Acid-Modified Polymers for Free-Radical Scavenging," Adv. Matter., 15(15):1291-1294 (2003).
75Spano, R., et al., "Substituted Anilides of 3-Monoethyl Ester of 4 Hydroxyisophthalic Acid," J. of Med. Chem., 15(5):552-553 (1972).
76Thompson, C. Ray, Stability of Carotene in Alfalfa Meal: Effect of Antioxidants, Industrial & Engineering Chemistry, 24(5): 922-925 (1950).
77Tsvetkov, O.N., et al., "Alkylation of Phenols with Higher Olefins. Part I," Int. Chem. Eng. 7(1):104-121 (1967).
78XP-002419239, "Discover Our World of Effects for Polyolefins," Ciba Speciality Chemicals, (2003).
Classifications
U.S. Classification564/158, 252/399, 252/407, 252/401, 426/601
International ClassificationC07C233/05, C09K15/16
Cooperative ClassificationC10N2230/10, A61Q1/00, A61K2800/522, C10M133/16, C10M2215/082, A61K8/42, C07C235/38
European ClassificationA61K8/42, C07C235/38, A61Q1/00, C10M133/16
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